Production of insecticidal composition of matter



Patented Mar. 16, 1954 ATENT OFFICE PRODUCTION OF INSECTICIDAL COMPOSITION OF MATTER Morton Kleiman and Arthur Goldman, Chicago,

Ill., assignors to Arve tion of Illinois y Corporation, a corpora- No Drawing. Application June 3, 1948 Serial No. 30,987

1 Claim. 1

This invention relates to the production of an insecticidal composition of matter.

More specifically, this invention relates to a novel method for preparing 1,4,5,6,7,8,8-hepta chloro 3a,4,7,7a tetrahydro 4,7 methanoindene using as a starting material the adduct of hexachlorocyclopentadiene and cyclopentadiene.

The adduct of hexachlorocyclopentadiene and cyclopentadiene can be prepared simply by intermixing said hexachlorocyclopentadiene and said cyclopentadiene preferably in the absence of additional solvent. The reaction proceeds in a satisfactory manner at room temperature and also may be accomplished at cooler or more elevated temperatures. The reaction is somewhat exothermic and the temperatures thereof should be controlled such that temperatures not exceeding about 200 C. and preferably not exceeding about 100-120 C. are maintained throughout the course of the reaction. The reactants may be utilized in a molar ratio of 1:1 however, an excess of either reactant can be present. The reaction product, namely the adduct of hexachlorocyclopentadiene and cyclopentadiene, is crystalline in nature and may be purified by recrystallization from a solvent such as methanol.

Thus, as a specific method for preparing the aforementioned adduct, hexachlorocyclopentadiene may be placed in a vessel equipped with a mechanical stirrer, thermometer and reflux condenser. lhe hexachlorocyclopentadiene may then be heated to about 70 C. and have added thereto in a portionwise manner an equal molar quantity of cyclopentadiene. The reaction temperature may be maintained at about 8 C. After the cyclopentadiene has been completely added, the stirring may be continued for several hours. The crystalline material thus formed may be purified by recrystallization one or more times from methanol.

The reaction of hexachlorocyclopentadiene and cyclopentadiene may be symbolized as follows:

pentadlene diene tetrahydro-4,7-methanolndene According to The Ring Index by Patterson andCapell, A, C s. Monograph $eries N o. 84,

l,4,5,6,7,8,B-heptachloro-3a.4.7,7a-tetrahydre4,7- methanoindenc and for the purpose of brevity and convenience, said product will hereinafter be referred to as l-chloro-chlordene.

In accordance with the present invention, l-chloro-chlordene may be formed by oxidizing chlordene with selenium dioxide (SeOz) in the presence of an organic acid, and treating the thus formed ester of chlordene and the acid utilized with hydrogen chloride in the presence of a catalyst and a small amount of water to result in the formation of the desired l-chlorochlordene.

The, process herein disclosed has many. ad,- vantages which will become more apparent by reading the following disclosure. Thus, the present invention provides a means to introduce a single chlorine atom into an olefinic molecule at a position known and definite, to result in a highly desirable and valuable material. In accomplishing this purpose,'extreme reaction conditions are completely avoided, thereby minimizing or substantially completely avoiding side reactions which might result in undesirable side products. As a result, overall yields as high as or even higher, based upon the theoretical amount possible, may be obtained. Thus, for

" every mole of chlordene used as starting material,

0.9 or more moles of l-chloro-chlordene may be recovered from the process.

The process of the present invention is of such a nature that the reagents utilized, such as the spent selenium dioxide, and the solvents, etc,,

Fol-

2,672,486 3 4 may be recovered and re-used in the process sufficient water must be added to initiate the reeither directly or with a minimum amount of action. As a matter of fact, there may be sufiitreatment. Further, said process is easily adaptcient water concommitant with the other reaced to commercial production. All the advantages tants to obviate the necessity for adding an adof this process as herein expressed or as evident 5 ditional amount. It is thus evident that only a from themztturethereofcombine to very. favorvery small: amount of WZtGIliSi necessary to iniably affect the" economies of the present-inventiate the reaction. A largeexcess of Water, while tion. permissible, is not desirable.

To facilitate an understanding of the nature Two moles of chlordene are oxidized per mole of the process, the reaction herein. involved is -of selenium-dioxide reduced, and consequently graphically illustrated as follows: thisfstoichiomet'ric ratio of reactants is preferred oi 01 Cl H ,0 H H C H seog-i-n-ps-on C1 H no1+nio H o1-o1 I --.-.Cl o1-o1 l a H G] H H TH you H 01 Ghloroden'c l-acyloxy-chlordcnc l-chloro-chlordenc The nature of R? as. above utilized as. an orbut not critical. Thusjifless'than thl"StOiCT1lO- ganic radical willlbe' more fully explained heremetric. amount. of selenium dioxide be utilized, inafter. then some of the chlordane will remaiirurr- The oxidation reaction herein involved is based changed when. the reaction is completed. 'Con onthe fact that selenium dioxide in the presence verseiy', if lessithanthestoichiometrio" amount'of or an. organiciacidan'd a small amount of water chlordene be utilized; thenexcess selenium diwill. react with .chlordene to form l-acyloxyoxide will remain in the reaction mixture after chlor'dene and metallic selenium. This maybe completion ofsaid' reaction. Since theselenium accomplished, for exampleyby adding sufiicient dioxide iswater soluble and since chlordane" is water" to the seleriiumdioxide such'that a'solunot, it is convenient'touse'aratio of reactants tionth'ereof ishb'tain'edi To the thus obtained which will result in thesubstantially-complete solution maybe'added ch'lordene and aoarboxylic conversion of chlorden'e to the oxidized product acid of relatively low molecular weight and relathereof, thereby obviating thenecessity for sep-' tively inert to the oxidizing effect of selenium arating' anyunreaotedohlordono"from fi dioxide, such as-acetic, propionic, butyric, or ished l chloro-chl'ordene; Thereforeya stoichiobenzoic acid. The temperature of reaction metric'amoun o p p fleXc S t o should be somewhat .aboveroom temperature and is p ifl' d- 'Toolarge oneness of Selenium will be naturallylimited' loy the decomposition 40 OXide o flw y because that temperature of:the. reactants or product. Genwhich 'does'not react issubsequently removed erally, temperatures between about 60 and about witha waterwash and is only more difiicultly re- 185 C. are applicable'randi temperatures between covelable; a more u y explained hereinabout 100 and 160 .C. aremore preferred. More after.

specifically, the application of "temperatures bent yp Organic acidutilized tween about 120 and130'C. provide a sati fa will next be considered. Theorganic acid used tory rate of reaction to. resultin excellent yields is-both a reactant and asolventfor the reaction of desired oxi'diz'e'dlmaterial' in relatively short mixtur h s, a preferred a t of d periods of time, jIt is thus convenient to utilize thatwhich will'j-ust-dissolve the reaction'mixanacid boiling within'the'above mentioned preture. An excess of acid is not harmful and will ferred range, such ias'acetic acid, thereby allowonly tend to afiect the rate of reaction because of mg" the reactionto proceed at the reflux t the dilution eii ect; conversely, smaller amounts perature of the mixture, and obviating the nethan the-minimum amount necessaryto dissolve cessity' for close temperature'control. the reactants completely may also be used to re- The ratio of reactants, themethod by which sult' in the desired product. It is therefore evi-f t ey may be intermixed, the operation during dent that the amount'of acid used is notcritical.

reaction, and thetime'" required are 'not'critical 'Asppr vious y s ted, t sa oeo should and may'bevaried quiteconsider'ably; beof relatively low molecular Weight and rela- The'reactants in the oxidation sta e m i tively inert to the oxidizing effect of selenium dichlordene, water; selenium dioxide-and an a id oxide. It is convenient and preferred that said asabove described; Itispre'ferred'that the water to acid should be relatively soluble i water su be added to the's'el'enium dioxide nd th t th that it can be removed from thereaction product chlordane and acid'be'then'addedito the selenium y y o with W "Further, the

dioxide=water mixture either together or inditwid-illiilizefdt shmflprefembll" a liquid at the vidually in any'order; however," the order and reaction temperature and be capable of dissolvmethod ofcombini-ngthereactants is'not'critical, o5 s e v r reactants substantially mp and it' is onlyn'ecessarythat they are intermixed. s wi h requiring the u ilizati n f un u "The amount clif'waterutilized is not critical; quantities of said acid. It is evident, therefore, however, it is'preferred to maintain the concenthat h c mm n, v ble ids u h a etic,

tration'of water at'a minimum. Thus, although propionio d uty acids are p r d? h wasmuch water'asis needed to dissol'vethe seleniover, various other acids can be used, h p

um dioxidecan'be utilized, an' excess'thereoi, or haps with less convenience, and the atu e of a smaller amount thereof will be satisfactory. these a s' naturally Suggest t s'elvesto since water 'isformed during the reaction'to the one sk d n the a n having wl d f extent -of-one mole of water per mole ofchlorthe 'pr fi t" d s osu deneoxidized. and este'rified', it is evident that only "The reaction"mixture withwhich we are prosently concerned does not require the use of a solvent other than the organic acid as hereinbefore related; however, the use of additional solvents in effectuating the reaction may at times be beneficial although generally is not preferred. The reaction may be carried out in the presence of such solvents as carbon tetrachloride, chloroform, benzene, toluene, hexane, pentane, dioxane, and the like. If an additional solvent be used, it is preferred that it be water soluble such that it can be separated from the reaction product by an aqueous extraction process. The use or additional solvent such as those suggested above may be advantageous in some instances, for example, if it is desired to minimize the amount of acid used, or if the acid has insufiicient solvency power, or possibly if the acid is not a sufficiently mobile liquid at the temperature of reaction.

The rate of reaction is dependent upon those factors which generally affect chemical reac tions. Therefore, varying the temperature of reaction and the concentration of reactants may affect the rate thereof. Generally, the reaction is completed after about 20 hours or perhaps less, depending upon the specific conditions utilized. Some product will have formed after only a very short period of reaction. Thus, at a reaction temperature of about 120-130 C., deposition of metallic selenium will have occurred after only about -15 minutes, thus indicating the formation of some 1acyloxy-chlordene within that period. The use of excess reaction time is not deleterious to the product, and hence, close control in this respect is not critical. The rate of reaction and extent of reaction can be fairly closely estimated by the rate of deposition of metallic selenium and by the quantity thereof deposited. If, for example, the reaction proceeds for a period of time between about one-half to twenty hours, the metallic selenium formed during the reaction can be removed from the mixture by filtration or any other means and the weight thereof can then be determined. If such a determination indicates that the reaction, although having proceeded, is incomplete, then additional reaction time can be allowed for the remaining mixture. It is expressly understood that the present invention is not dependent upon, nor limited to, the reaction proceeding to completion, or even substantial completion. It is preferred, however, that such be the case inasmuch as it results in a more economical operation.

Where the oxidation reaction of chlordene as hereinbefore described is completed or has otherwise been stopped, the mixture contains, among other materials, the ester of chlordene and the organic acid utilized, previously symbolized as 1-acyloxy-chlordene. Further, the reaction mixture contains as a precipitate metallic selenium which can easily be removed by filtration, cent'rifuging, decanting of supernatant liquid, or by any other means known to the art. It is preferred that the metallic selenium be removed at this point, and, as a material economical aid, it can be reconverted to selenium dioxide by means well known to the art and subsequently re-utilized in the process as hereinbefore described.

The ester formed according to the present process need not be isolated preparatory to converting it to the desired l-chloro-chlordene as hereinafterdescribed, nor is'it essential that any other material contained in the reaction mixture such a rate that the mixture is substantially saturated therewith during the course of the reaction.

Friedel-Crafts type catalysts such as aluminum chloride (A1013), ferric chloride (FeCls), antimony pentachloride (SbCl5), boron trifiuoride (BFs), zinc chloride (ZnClz), titanium tetrachloride (TiCh), hydrogen fluoride (HF), sulfuric acid (H2804), phosphoric acid (H3PO4), phosphorous pentoxide (P205), stannic chloride (SnCh) boron trichloride (BCh) aluminum bromide (A1BI3) and like materials may be utilized.

The reaction whereby l-acyloxy-chlordene is converted to l-chloro-chlordene is generally carried out at temperatures between about room temperature and about 185 0.; however, temperatures between about 60 and 160 C. are preferred. More specifically, the application of temperatures between about and C. provides a satisfactory rate of reaction to result in excellent yields of the desired, valuable product.

A preferred method of procedure is to saturate the reaction mixture with hydrogen chloride while said mixture is at room temperature, to then add the catalyst, and subsequently to bring the reaction mixture to the desired temperature while passing hydrogen chloride through the mixture at such a rate as to maintain a substantially saturated solution thereof during the course of the metathetical reaction.

The procedure is not limited to this preferred method however. Thus, the relative times at which the catalyst and hydrogen chloride are introduced are not critical, nor is it essential that the hydrogen chloride be first introduced at room temperature. The rate of introduction and passage through the reaction mixture of hydrogen chloride is not critical. If the rate of introduction be slow, then the reaction will be correspondingly of a slower rate. If the rate of introduction be increased then the rate of reaction will be increased. Any excess hydrogen chloride introduced may be vented from the reaction vessel, however, from an economical viewpoint it is desirable that any excess be kept at a minimum.

As in the oxidation step, previously described, it is convenient to carry out the metathetical reaction presently described at the reflux tentperature of the reaction mixture. Therefore, if an acid such as acetic acid were the solvent originally used, allowing the reaction to proceed at the reflux temperature, which is within the preferred range of operation, obviates the neces sity for close temperature control.

In the step of converting the chlordene ester to l-chloro-chlordene, as well as in the prior oxidation stage, it is desirable that the reaction mixture be stirred, and that any other means commonly used to facilitate'chemica-l reactions be used. Thus, the advantage of introducing'hydrm gen, chlorideintoethe reaction mixture inner-manner such that it is dispersed ithroughout the.

of the acyloxy group witha chlorine atom. is

efiected is. relativelyrapid, and generally the desired product will form between about 15-minutes and about hours. Itiis, of course, obvious that the rate of reaction. is. .dependenton-- those usual. factors suchas temperature, concentration of. reactants, efiiciency of .stirring and -the like. Thus, in the: lower-temperature range, the reaction is slower. than-at. more. el'evated tempera tures,.-and. the rate of. reaction. is. also. slower if. the... concentration .of reactants be diminished. It. hasJoeen. found that. a. reactiontime of: about 4 to 6 hours at a. temperature of about 120.7130 0.. will. result. in a. practically quantitative yield of L-chloro-chlordene where the leveloi hydrogen.

chloride was. maintained at or near. .the. saturationpoint of. the reaction mixture. .-.Excess.- time ofreaction isnot deleterious and-consequently the. reaction need-.not. necessarily be. stopped. at. or. near completion. Eurthenthe reactionmay be abated before conversion is complete. Howevensince the reactiontima for achieving. complete conversion is not excessive, it is economical and. preferred. that sufilcient time be allowed to substantially completely convert. allof the lacyloxy-chlordene. to .1.- chloro-chlordene.

As a non-fully equivalent alternative, the. hydrogen chloride in the reaction previously described maybe introduced in the form of its aqueous solution such as concentrated hydrochloric acidor fuming hydrochloric acid. The amount of hydrochloric acid used will depend on the amount of chlordene ester which is to be converted, and a stoichiometric excessoi hydrochloric acid is preferred. Said acid is. preferably added portionwise during the course of the .reaction, such that a suflicient amount of H61 is constantlypresent in the reaction mixture to maintain said reaction at a reasonable rate.

The l-chloro-chlordene prepared according to the present process may be recovered fromthe final reaction mixture in a relatively easy'manner. Generally, the reaction mixture will contain 1- chloro-chlordene, which is not water soluble, and various other materials such as a low molecular weight acid, possibly some selenium dioxide, some hydrogen chloride and various other water soluble materials. Hence, itis merelynecessary to add water tothe reactionmixture precipitate the desired l chloro-chlordene which can then be filtered to result in. the solid, isolated, desired product which may'notrequire furtherpurincation.

Alternativelyboth water and an organic'solvent not miscibletherewith,;such as carbon tetrachloride, benzene, heptane; chloroform, isopropyl ether, ethyl acetate, and the like, maybe addedto thereaction' mixture. The water-soluble materialwill be contained in'the waterlayer and the l-chloro-chlordene in the organic layer. The two layers can then be separated, and theorganic solvent can then be removed from the desired product by evaporation, distillation, or the like.

If the organicacid of a relatively low molecular weight utilized in the oxidation reaction beinsufiiciently soluble in water tob'e effectively extracted therewith, then it may be advantageous to distill either at atmosphericor invacuo all or a portion of theacid'contained in'themixture, Alternativemthe acid maybe allowed toiremain' in the reaction mixture. toseparate out" upon the additionof-water. The entire. mixture may then be filtered torecover whatever .-1.-chlorochlordene. may have, precipitated, and then the:

acid layer may be distilledto recover the l-chlorochlordene remaining dissolved therein. Extraction with. dilute aqueousalkali will also. effectively remove any acid. which is only d-ifficultly. soluble.

in l. water.

Ordinarily, the .l-chloror-chlordene reco'veredas herein described is pure enough to be utilized. without further treatment. Probableimpurities.

The following example is forthepurposeofl illustrating the present invention, without, however, restricting it thereto.

Example Toa reaction vessel equipped with a; stirrer and reflux condenser was added 19 parts (by weight) selenium dioxide and 5 parts' (by weight) water. The mixture was heated to dissolve the selenium dioxide and 157 parts (by weight) acetic acid was added to the selenium dioxide-water mixture. Then 102 parts (by weight) chlordene was added to the reaction vessel. The mixture thus obtained was heated to reflux temperature and so maintained fora period of 22 hours. At that time the mixture was filtered to remove the. precipitated metallic selenium, and then placed in a similar reaction vessel as previously described and further equipped with a gas inlet tube extending to the bottom thereof and having attached thereto a sintered glass dispersion'piece. Dry hydrogen chloride gas was passed through the reaction mixture, and while being stirred, the

- mixture was heated to reflux temperature. Zinc chloride (37 parts by weight) was then added to the mixture, and the flow of hydrogen chloride was continued at such a rate as to maintain a saturated solution thereof at the reflux temperature. After 6 hours the flow of hydrogen-chloride was discontinued and the mixture was allowed to cool to room temperature. Sufficient water and isopropyl other were then added to substantially completely dissolve all of the reaction mixture. The two layers were separated and the other layerwas extracted once with water and then twice with 5% aqueous sodium hydroxide and then once again with water. The thus'extracted ether solution was dried with calcium chloride, treated with Nuchar, filtered and concentrated by evaporation almost to dryness. The residue was then dissolved in pentane'and-crystallized therefrom. l-chloro-chlordene, fairly pure, and only slightly discolored, was obtained inthe amount of 86.6 parts (by weight) in the first crop of crystals- .A second 'crop of crystals amounted to 9.7 parts of 1-chIoro-chlordene, thereby yieldinga total of 95.3'parts' by weight. or about an 35% yield based on the original amount of chlordene utilized.

The product at this stage was of a sufilcient purity for utilization without.furthertreatment; however, to .remove the slight discoloration the product was dissolved'in .pentane and..passed through a .coliunnpacked with .67 parts. (by

If desired, the product may .be.

weight) of Florex. The column was then eluted with more pentane, and the pentane fractions were then combined and evaported to dryness to result in pure, white, crystalline l-chlorochlordene. The amount of product recovered from the Florex column was almost equal to that introduced, thereby indicating the purity of the material prior to Florex treatment.

It is thus seen that the process herein disclosed has many advantages. No complex equipment is necessary; no intermediate products need be iso lated or otherwise purified; the absence of undesirable side reactions insures excellent yields of product; extreme reaction conditions are avoided; and the final product is easily isolated in a relatively pure state.

The product obtained from the process of the present invention exhibits a very high order of toxicity toward a large variety of insects and similar forms of life, and its value is further enhanced by the fact that it exhibits residual toxicity-that is, a retention of insecticidal potency for a considerable length of time after being deposited on exposed solid surfaces. This latter property considerably increases the value of an insecticidally active compound for many types of applications.

l-chloro-chlordene may be utilized in the form of oil sprays, dusts, aqueous emulsions, aerosols, etc., either alone or in association with any other desired toxicants or carriers, in preparations and by methods of application known to the art.

We claim as our invention:

The method which comprises reacting 4,5,6}?,8,8-hexachloro-3a,4,7,7a-tetrahydro 4,7-

methanoindene in the presence of water with selenium dioxide and acetic acid, said acid being present in an amount adequate to substantially completely dissolve the reactants, at the reflux temperature of said reaction mixture to form the l-acyloxy derivative thereof, separating precipitated metallic selenium, reacting said derivative while retaining it in the remaining resulting reaction mixture with hydrogen chloride in the presence of zinc chloride at the reflux temperature of the latter reaction mixture to convert said derivative to 1,4,5,6,7,8,8 heptachloro- 3a,4,7,7a-tetrahydro 4,7 methanoindene, and separating and recovering the latter as the product of the process.

MORTON KLEIMAN.

ARTHUR GOLDMAN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,395,452 Bruson Feb. 26, 1946 2,418,708 Gwynn et a1 Apr. 8, 1947 2,481,159 Schmerling Sept. 6, 1949 2,519,190 Hyman Aug. 15, 1950 2,528,655 Herzfeld et a1. Nov. 7, 1950 2,576,666 Bluestone et al. Nov. 27, 1951 FOREIGN PATENTS Number Country Date 686,849 Germany Jan. 17, 1940 OTHER REFERENCES Stein: "Angewandte Chemle, vol. 54, pp. 146 152 (1941). 

